Preparation of aminopropionitriles



Patented Aug. 12, 1947 Mm; j; v mnrammox or AMINOPROPIONITRILES i 1 1New york, N. Y.,-aiid rising, n; I

Cyanamid Comm,

notation of Maine ammuauau... saturates; ,sen rmsegua v (01. zoo-12m Thepresent invention're'lates tothe production oi' amirionitriles and moreparticularly we method 01' preparinz VII-substituted p-aminopropionitriles which conform to the general formula NCHrCHr-CN n'i wherein R represents an alkyl radical, R represents either. hydrogenor an alkyl radical, and R and R when taken together with the nitrogenatom represent a heterocyclic ring.

We have discovered that amino compounds 0 the above type may be obtainedby reacting a fi-alkoxypropionitrile with either a primary or secondaryalkyl amine or a heteroeyclic amine which contains a hydrogen atomconnected to nitrogen such as, for example, piperidine, morpholine,piperazine, a-pipecoline, anabasine and the like.

Typical reactions may be illustrated as follows:

OHr-Cr CHs-CH,

CHr-C The amine and the alkoxypropionitrile when heated together in apressure vessel at temperatures ranging from 150 to about 230 C. reactreadily to produce the B-aminopropionitrile.

. The reaction may be carried out in the pres- The followin: specificexamples will further illustrate the invention.

a were for "hours: The reaction product was distilled under reducedpressure. p-dimethylaminopropionitrile, B. P. C./29 mm., was obtained ina yield oi 88.3%.

Example 2 A mixture consisting of grams (1 mol) of plperidine and 85grams (1 mol) oi p-methoxypropionitrile was heated in a closed vessel at200 C. for 3 hours. Distillation oi. the reaction product under vacuumgave grams (79.7% yield) 01 ,6-N-piperidinopropionitrile, B. P. 123.5C./26 mm.

Example 3 38 grams of morpholine and 35.2 grams oi,a-methoxypropionitrlle were heated in an autoclave at 190-200 C. for 3hours. Distillation of y the reaction product gavep-N-morpholinopropioence of solvents or diluents such as, for example,

dibutyl ether, dioxane, carbon tetrachloride, cycloaliphatic or aromatichydrocarbons, or miscible mixtures thereof.

nitrile boiling at -150 C./26 mm.

Example 4 09 grams or p-ethoxypropionitrile and 85 grams or plperidinewere heated in an autoclave at 200- 210' C. for 8.5 hours. Distillationof the reaction product under reduced pressure gave 80 arams (58%;yield) of p-N-piperidin proplonitrile.

, Example 5 85 grams of p-methoxypropionitrile and 73 grams ofn-butylamine were heated in a closed vessel at -190 C. for 3.5 hours.The reaction product was distilled under vacuum. 62 grams ofp-n-butylaminopropionitrile, B. P. 119 C./26 mm., were obtained.

Example 6 A mixture consisting of 129 grams of .dl-nbutylamine and 71grams or p-methoxypropim nitrile'was heated in an autoclave at -200 C.

for 3 hours. Distillation of the reaction product under reduced pressuregave p-(di-n-butyl- 50 amino) propionitrile boiling at 97-l03 C./2 mm.

Example 7 59.6 grams oi. piperidine and 159 grams ofdodecoxypropionitrile were heated together for 5 hours in an autoclaveat 200 C. The product.

